US3210191A - Silver halide emulsions sensitized with alkylene oxide polymers - Google Patents

Silver halide emulsions sensitized with alkylene oxide polymers Download PDF

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Publication number
US3210191A
US3210191A US149850A US14985061A US3210191A US 3210191 A US3210191 A US 3210191A US 149850 A US149850 A US 149850A US 14985061 A US14985061 A US 14985061A US 3210191 A US3210191 A US 3210191A
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Prior art keywords
silver halide
compounds
alkylene oxide
emulsion
formaldehyde
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US149850A
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English (en)
Inventor
Willems Jozef Frans
Thiers Robrecht Julius
Munck Joseph Louis De
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Gevaert Photo Producten NV
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Gevaert Photo Producten NV
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/04—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with macromolecular additives; with layer-forming substances
    • G03C1/043—Polyalkylene oxides; Polyalkylene sulfides; Polyalkylene selenides; Polyalkylene tellurides

Definitions

  • these polyglycols and alkylene oxide polymers should possess a molecular weight of at least 400 and, in order to obtain a noticeable effect it is in practice necessary to use compounds which possess a molecular weight of 1500 to 2000 and more.
  • the developability of lightsensitive emulsions can favourably be influenced by adding to one or more emulsion layers or other layers, belonging to the photographic material, compounds obtained by the polycondensation of low molecular alkylene oxide derivatives, which of themselves have little activity with aldehydes and polyamines.
  • aldehyde or compounds which are able to split off formaldehyde such as p-formaldehyde, trioxymethylene or hexamethylene tetramine are preferred as aldehyde compounds.
  • aldehyde compounds include aliphatic aldehydes such as acetaldehyde and croton aldehyde, and as aromatic aldehyde e.g. benzaldehyde can be used; as heterocyclic aldehyde e.g. furfural can be employed. It is evident that also mixtures of aldehydes may be used in preparing the above mentioned ter-condensates.
  • aliphatic amines such as ethylene diamine also aromatic or heterocyclic amines such as melamine (2,4,6- triamino-1,3,5-triazine), diamino methyltriazine, guanazole and others, as well as mixtures of polyamino compounds are considered as dior polyamino compounds.
  • An example of a favourable proportion of reagents is egg. 1 mol of polyamine, 3 to 6 mols of aldehyde and 2 mols of lower polyoxy alkylene compounds.
  • the condensation is realized by mixing the three basic products and heating under stirring to about C. When the mixture forms a homogeneous mass the temperature is raised to 150 C. and the formed water is distilled off. Sometimes it is desirable to eliminate more thoroughly the water split off during the condensation, by carrying out the reaction under reduced pressure some moments before stopping the heating.
  • PREPARATION 2 In a three-necked flask, provided with a stirrer, a thermometer and a condenser, 2.5 g. (0.2 mol) of 2,4- diamino-6-methyl-l,3,5-triazine are mixed with 9 g. (0.12 mol) of a 40% aqueous solution of formaldehyde and 40 g. (0.04 mol) of polyoxy ethylene glycol with molecular weight of 1,000 before heating. Whilst stirring this mixture is heated to 85 C. for 10 min. Then the temperature of the reaction mixture is raised to 130 C. in 4 h., while 7 cm. of water are distilled'ofl.
  • PREPARATION 3 In a three-necked flask, provided with a stirrer, a thermometer and a condenser, 3 g. (0.05 mol) of ethylene diamine are mixed with 15 g. (0.2 mol) of a 40% aqueous solution of formaldehyde and 100 g. (0.1 mol) of polyoxy ethylene glycol with molecular weight 1,000 before heating. Whilst stirring this mixture is heated to 85 C. for min. Then the temperature of the reaction mixture is raised to 130 C. in 4 h., while 10 cm. of Water are distilled off. The residue is poured out into a fiat dish for cooling. 102 g. of a light-brown waxy product are obtained.
  • the compounds according to the present invention may be added to the emulsions or they may be brought into intimate contact with the silver halide emulsion layers, either by dissolving them in water or in an aqueous mixture of organic solvents which do not disadvantageously influence the silver hailde emulsions and whereafter the solutions obtained is added to an emulsion or applied to an emulsion layer as a coating composition.
  • the compounds can be introduced into the emulsion at various stages during its preparation; for example, they may be incorporated as a separate addition, or mixed with one or more of the other ingredients used at the first precipitation of the silver halide grains, during the physical or chemical ripening process, or at some other point prior to coating the emulsion. Preferably, they are added after the chemical ripening and just before coating the emulsion.
  • the optimum amount of the compound to be added to the emulsion depends on the particular compound chosen, the nature of the colloid binding agent for the silver halide grains and the amount and kind of silver halide in the emulsion. In general, however, the compounds according to the invention are added in a quantity of 100 mg. to 10 g. per mol silver halide. If necessary, however, still other quantities of these compounds can be added which fall outside these limits.
  • the process of the present invention can be combined with a method for increasing the sensitivity of photographic material by incorporating therein small amounts of a sulphur-containing compound, such as allyl isothiocyanate, allyl thiourea and sodium thiosulphate, small amounts of reducing sensitizers such as the tin compounds described in Belgian specifications Nos. 493,464 and 568,- 687, the imino-aminomethane sulphinic acid compounds described in British specification No. 789,823 or small amounts of noble metal compounds such as of gold, platinum, palladium, iridium, ruthenium and rhodium.
  • the new process is advantageously combined with the sensitizing action of compounds originally present in gelatin.
  • stabilizing agents such as, for example, mercury compounds and the compounds claimed and referred to in the statement of prior art of Belgian specifications Nos. 571,916 and 571,917 may be added to the emulsion. It is also usual to sensitize and/ or to stabilize silver halide emulsions by incorporating therein cadmium salts or by carrying out their processing in the presence of cadmium salts.
  • the compounds of the present invention can further be combinedwith oniurn compounds such as ammonium, sulphonium or phosphonium compounds. Still other ingredients such as anti-fogging agents, colour couplers, developing substances, hardening and wetting agents, can moreover and without deleteriously alfecting the emulsion, be added thereto in a manner known to those skilled in the art.
  • the new compounds are effective in inc Hydroquin-one creasing the X-ray sensitivity and the general light-sensitivity of orthochromatic, panchromatic, and all special emulsions, as well as the ordinary non-spectrally sensitized ones.
  • they can be added without or with optical sensing dyes but in the latter case not together with these dyes.
  • They are also useful with a variety of emulsions, since a pronounced increase of speed is obtained in either negative or positive types of emulsions.
  • the method according to the present invention is especially appropriate for the treatment of gelatin silver halide emulsions, the invention is not limited to such colloid emulsions.
  • Emulsions based on other waterpermeable colloids may also be treated according to the present invention.
  • colloids are e.g.
  • the new developing accelerators may be used for sensitizing the known types of silver chloride, silver bromide, silver iodide emulsions and emulsions containing mix tures of these halides.
  • the methods as described in the above examples are not limited, as far as the quantity and the nature of the developing accelerator to be added or the moment of the addition are concerned. Indeed, for obtaining an optimum elfect, all particular techniques in the preparation of light-sensitive emulsions should be taken into account.
  • An advantage of this invention is the compatibility of the new developing accelerators with colour couplers and optical sensitizing dyes, which fact is of great importance for using the new developing accelerators to increase the general light-sensitivity of colour photographic material containing one or more light-sensitive layers.
  • a further advantage of the material according to the present invention resides in its simple application such as e.g. in the manufacture of light-sensitive materials for amateur and professional photography and cinematography, in graphic proceses and in scientific and industrial applications.
  • Example I A washed coarsely grained gelatin silver iodobromide negative type of emulsion (average grain size 0.8a) wherein the silver halide consists of 94.5 mol percent silver bromide and 5.5 mol percent silver iodide is ripened at 45 C. After addition of a panchromatic sensitizing dye and other usual ingredients the emulsion is coated onto a suitable support (sample 1). Further samples were prepared by adding, prior to coating, to the same emulsion and per mol silver halide present the amounts of developing accelerators listed below. They are then treated as sample 1. After drying and exposure they are developed for 7 min. at 20 C. in a solution consisting of:
  • Sensitometric results such as 5-hydroxy-7-methyl-s-triazolo-(4,5a)-pyrimidine and of other usual ingredients, the emulsion is coated onto a suitable support (sample 1).
  • Added developing Added Relative Further samples are prepared by adding to the same sample accelerator amount, Gamma FOE 5 emulsion, prior to Coating, and, per mol silver halide y present, the amounts of developing accelerators listed 1 P01 ow ethylene 100 0 43 O below. They are then treated as sample 1. After drying 1yco1with and exposure they are developed for 4 min. into a solution g ht 1 000 1a g g 82 3g 0. 1? 1 consisting of. 1b. .4 1 0. 0. 0.
  • Example 3 We claim: l.
  • a light-sensitive photographic material comprising ed as in i g i f 312 323: 5 fig z gfiiz g gg g min at a support and at least one gelatmo silver halide emulsion i followin dgvefo er layer containing an alkylene oxide polymer in an amount g p Grams between 100 mg. and 10 g.
  • said alkylene oxide polymer bein a water soluble product of 0.5 P go d ifi r r i ii l l h i e ti taili di 100 V the simultaneous condensation of a polyalkylene glycol H dro uingne y n 5 50 having a molecular weight of less than 1500 formaldehyde g gzg iz fii gg u 80 and an organic polyarnine having at least two amino Potassium bromide y u 2 groups, each with an active hydrogen atom thereon, said Citric acid 2 formaldehyde being present in an amount having a molar Wateru 616662;; ratio relative to the combined amounts of glycol and polyarnine of about 0.5:1 to 2:1.
  • Sensrtometrrc results: 2.
  • a light-sensitive photographic material comprising a support and at least one gelatino silver halide emulsion S 1 Add d d e p aggi s g v Gamma F0 layer containing an alkylene oxide polymer in an amount amp e am em or tivity g between 100 mg. and 10 g.
  • said alkylene oxide polymer being a water soluble product of 1 100 0.70 0.16 the simultaneous reaction of 2 mol of a polyalkylene 2 g gggg gg f 119 M9 17 glycol having a molecular weight less than 1500 and 3 to 3 tlo 3.4 1 6 mols of formaldehyde and 1 mol of an organic polyamine having at least two amino groups, each with an Example 4 active hydrogen atom thereon.
  • a hght-sensitlve P g p c material comprising emulsion wherein the silver halide consists of 98.2 mol a PP and atleast one l d hallde 51111151911 percent silver bromide and 1.8 mol percent silver iodide is layer, said emulsion layer being 1n intimate contact With ripened at 42 C.
  • an alkylene oxide polymer wh1ch is a water-soluble prod- 7 55 not of the simultaneous reaction of a polyalkylene References Cited by the Examiner glycol having a molecular Weight of less than 1500, UNITED STATES PATENTS formaldehyde and an organic polyamine having at least 1 970 578 8/34 Schoener et al 260468 two amino groups, each with an active hydrogen atom 2:716:O62 8/55 Carroll et a1- thereon, said formaldehyde being present in an amount having a molar ration relative to the combined amounts of NORMAN TORCHIN, Primary Examine!- glycol and polyamine of about 0.5:1 to 2: 1. LOUISE P. QUAST, Examiner.

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Polyamides (AREA)
US149850A 1960-11-04 1961-11-03 Silver halide emulsions sensitized with alkylene oxide polymers Expired - Lifetime US3210191A (en)

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BE (1) BE609944A (cs)
DE (1) DE1179804B (cs)
GB (1) GB940051A (cs)
NL (2) NL257624A (cs)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3516844A (en) * 1966-07-28 1970-06-23 Eastman Kodak Co Coating of gelatin silver halide photographic emulsions
EP0112162A2 (en) 1982-12-13 1984-06-27 Konica Corporation Light-sensitive silver halide photographic material
EP0124795A2 (en) 1983-04-11 1984-11-14 Fuji Photo Film Co., Ltd. Silver halide photographic emulsion
US6071688A (en) * 1998-07-29 2000-06-06 Eastman Kodak Company Providing additives to a coating composition by vaporization
US7250202B1 (en) 1998-06-18 2007-07-31 Ilford Imaging Ch Gmbh Recording sheets for ink jet printing

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1970578A (en) * 1930-11-29 1934-08-21 Ig Farbenindustrie Ag Assistants for the textile and related industries
US2716062A (en) * 1953-07-01 1955-08-23 Eastman Kodak Co 4-hydroxy-6-alkyl-1, 3, 3a, 7-tetrazaindene stabilizers for emulsions sensitized with alkylene oxide polymers

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1970578A (en) * 1930-11-29 1934-08-21 Ig Farbenindustrie Ag Assistants for the textile and related industries
US2716062A (en) * 1953-07-01 1955-08-23 Eastman Kodak Co 4-hydroxy-6-alkyl-1, 3, 3a, 7-tetrazaindene stabilizers for emulsions sensitized with alkylene oxide polymers

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3516844A (en) * 1966-07-28 1970-06-23 Eastman Kodak Co Coating of gelatin silver halide photographic emulsions
EP0112162A2 (en) 1982-12-13 1984-06-27 Konica Corporation Light-sensitive silver halide photographic material
EP0124795A2 (en) 1983-04-11 1984-11-14 Fuji Photo Film Co., Ltd. Silver halide photographic emulsion
US7250202B1 (en) 1998-06-18 2007-07-31 Ilford Imaging Ch Gmbh Recording sheets for ink jet printing
US6071688A (en) * 1998-07-29 2000-06-06 Eastman Kodak Company Providing additives to a coating composition by vaporization

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GB940051A (en) 1963-10-23
NL109731C (cs)
DE1179804B (cs)
BE609944A (cs)
NL257624A (cs)

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